CN101891862A - Modified terpene resin and preparation method thereof - Google Patents
Modified terpene resin and preparation method thereof Download PDFInfo
- Publication number
- CN101891862A CN101891862A CN 201010258704 CN201010258704A CN101891862A CN 101891862 A CN101891862 A CN 101891862A CN 201010258704 CN201010258704 CN 201010258704 CN 201010258704 A CN201010258704 A CN 201010258704A CN 101891862 A CN101891862 A CN 101891862A
- Authority
- CN
- China
- Prior art keywords
- modified terpene
- pentadiene
- terpene resin
- firpene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a modified terpene resin and a preparation method thereof. The modified terpene resin is a compound prepared from pinene and pentadiene through copolymerization. The modified terpene resin comprises the following components in percentage by weight: 40 to 80 percent of pinene, 20 to 60 percent of pentadiene, alchlor that is present in an amount of 4 to 5 percent of the total weight of the two monomers, and 0.0001 to 0.001 percent of pentaerythritol ester antioxygen. The preparation method comprises the following steps of: polymerizing the raw materials of pinene, pentadiene, alchlor catalyst, pentaerythritol ester antioxygen and the like in methylbenzene at the temperature of between -10 and 10DEG C for 2 to 8 hours with continuous stirring, wherein the weight of the methylbenzene is 0.8 to 1.0 time the total weight of the monomers; and washing, separating and drying to obtain the modified terpene resin. The preparation method has the advantages of easy control of reaction conditions, high yield of polymerization and good resin quality.
Description
Technical field
The present invention relates to a kind of modified terpene resin and preparation method thereof, especially by a kind of modified terpene resin of firpene and m-pentadiene copolymerization and make each method.
Background technology
Terpine resin claims polyterpene or pinene resin again.It mainly is to utilize terebinthine α-Pai Xi or beta-pinene, under Ke Shi catalyst action not, through cationoid polymerisation and a series of simple linear polymers from liquid to the solid.Because of having good physicals such as nontoxic, hydrophobic, non-crystallizable, electrical isolation, tackify and acid and alkali-resistance, excellent in chemical performance such as anti-aging, be soluble in aromatic hydrocarbon and vegetables oil, be a kind of good tackifier, be widely used in fields such as rubber, plastics, printing ink, coating, weaving, tackiness agent, pressure sensitive adhesive, cable, color printing, paint, packing, slushing oil, foodstuffs industry.But along with ecological environmental protection and terebinthine output reduce year by year, causing with turps is that the terpine resin of main raw material is produced the atrophy year by year of its output.People to be being the exploitation dynamics that has strengthened petroleum resin, the 2nd, one after another terpine resin is carried out modification, the modified terpene resin preparation method is numerous and diverse mostly at present, kind and specification still seldom, quality is not high, performance often can not satisfy the requirement of high-quality tackiness agent.
Summary of the invention
In order to overcome the deficiency of existing modified terpene resin and preparation method thereof, the invention provides a kind of a kind of modified terpene resin by firpene and m-pentadiene copolymerization and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is: a kind of modified terpene resin and preparation method thereof is characterized in that: it is the compound that obtains by by firpene and m-pentadiene copolymerization;
The weight percent moiety of the present invention's prescription is as follows:
The 40-80%wt firpene; The 20-60%wt m-pentadiene;
The 4-5%wt aluminum trichloride catalyst of above-mentioned two raw material total amounts;
0.0001-0.001%wt pentaerythritol ester oxidation inhibitor.
Its processing condition are: be medium with toluene, polymerization in toluene, the weight of toluene be above-mentioned firpene, m-pentadiene, aluminum chloride, pentaerythritol ester gross weight 0.8-1 doubly, drop into firpene, m-pentadiene, pentaerythritol ester oxidation inhibitor, temperature-5-10 ℃, constantly stir during polymerization, feed intake polymerization reaction time 2-8 hour continuously or intermittently.
In container, add firpene, m-pentadiene, aluminum chloride, pentaerythritol ester gross weight 0.8-1 toluene doubly, with toluene is medium, polymerization in toluene, polymerization temperature-5-10 ℃, pressure is normal pressure, more a certain amount of firpene, m-pentadiene, aluminum chloride, pentaerythritol ester oxidation inhibitor is slowly splashed in the reaction mixture, drips off in 30-45 minute, constantly stir stirring reaction 2-8 hour during polymerization;
Above-mentioned modified terpene resin preparation method step is as follows:
Step 1: in the exsiccant there-necked flask, add an amount of toluene, aluminum chloride, control is bathed temperature at-5-10 ℃, again an amount of firpene, m-pentadiene, pentaerythritol ester oxidation inhibitor raw material are slowly splashed in the reaction mixture, dripped off in 30-45 minute, stirring reaction 2-8 hour.
Step 2: reaction mixture is washed with 70-90 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get the faint yellow solid modified terpene resin.
Product color of the present invention (Gardner's method Garder)≤6
Acid number (mg KOH/g)≤1.0
Toluene insolubles (w/w%)≤0.05
Softening temperature (ring and ball method, ℃, the trade mark/specification) TP2086 86 ± 3
TP2095 90-99
TP2105 100-109
TP2115 110-119
Can be dissolved in aromatic hydrocarbons, acetic ester etc.
The invention has the beneficial effects as follows that prescription of the present invention and processing condition are optimized, polymkeric substance is after washing, removing solvent, residual monomer, oligopolymer, and the polymerization total recovery reaches more than 88%; Preparation method's reaction conditions of the present invention is easy to control, polymerization yield height, can make the better tackifying resin of quality, be widely used in adhesive industry, have good consistency with thermoplastic elastomer, natural rubbers such as SIS, SEBS, APP, be applicable to that preparation is the tackiness agent of base-material with SIS, other elastomericss of Polyolefin and.
The present invention is further described below in conjunction with embodiment.
Embodiment one:
Step 1: in exsiccant 500ml there-necked flask, add 80g toluene, 4g aluminum chloride, control are bathed temperature at-10 ℃, slowly splash into 40g firpene, 60g m-pentadiene, 0.0001g pentaerythritol ester oxidation inhibitor in the reaction mixture again, dripped off stirring reaction 2 hours in 30 minutes;
Step 2: step 1 reaction mixture is washed with 70 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 80g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment two:
Step 1: in exsiccant 500ml there-necked flask, add 90g toluene, the 4.5g aluminum chloride, control is bathed temperature at-5 ℃, 50g firpene, 50g m-pentadiene, 0.002g oxidation inhibitor is slowly splashed in the reaction mixture again, drips off stirring reaction 3 hours in 35 minutes;
Step 2: step 1 reaction mixture is washed with 75 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 82g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment three
Step 1: in exsiccant 500ml there-necked flask, add 100g toluene, the 4.5g aluminum chloride, control is bathed temperature at 0 ℃, 60g firpene, 40g m-pentadiene, 0.002g oxidation inhibitor is slowly splashed in the reaction mixture again, drips off stirring reaction 4 hours in 40 minutes;
Step 2: step 1 reaction mixture is washed with 80 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 85g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment four:
Step 1: in exsiccant 500ml there-necked flask, add 100g toluene, 5g aluminum chloride, control are bathed temperature at 5 ℃, slowly splash into 55g firpene, 45g m-pentadiene, 0.0004g pentaerythritol ester oxidation inhibitor in the reaction mixture again, dripped off stirring reaction 5 hours in 40 minutes;
Step 2: step 1 reaction mixture is washed with 85 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 88g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment five:
Step 1: in exsiccant 500ml there-necked flask, add 100g toluene, 5g aluminum chloride, control are bathed temperature at 8 ℃, slowly splash into 60g firpene, 40g m-pentadiene, 0.0006g pentaerythritol ester oxidation inhibitor in the reaction mixture again, dripped off stirring reaction 6 hours in 40 minutes;
Step 2: step 1 reaction mixture is washed with 85 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 88g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment six:
Step 1: in exsiccant 500ml there-necked flask, add 100g toluene, 5g aluminum chloride, control are bathed temperature at 10 ℃, slowly splash into 70g firpene, 30g m-pentadiene, 0.0008g pentaerythritol ester oxidation inhibitor in the reaction mixture again, dripped off stirring reaction 7 hours in 45 minutes;
Step 2: step 1 reaction mixture is washed with 80 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 86g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Embodiment seven:
Step 1: in exsiccant 500ml there-necked flask, add 100g toluene, 5g aluminum chloride, control are bathed temperature at 10 ℃, slowly splash into 80g firpene, 20g m-pentadiene, 0.001g pentaerythritol ester oxidation inhibitor in the reaction mixture again, dripped off stirring reaction 8 hours in 45 minutes;
Step 2: step 1 reaction mixture is washed with 90 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get faint yellow solid modified terpene resin 80g;
The monomer metering drops into continuously in the enforcement, helps technology controlling and process.
Claims (3)
1. modified terpene resin, it is characterized in that: it is the compound that is obtained by firpene and m-pentadiene copolymerization;
The weight percent of modified terpene resin prescription consists of:
(1) 40-80%wt firpene;
(2) 20-60%wt m-pentadiene;
(3) the 4-5%wt aluminum chloride of above-mentioned two raw material total amounts;
(4) 0.0001-0.001%wt pentaerythritol ester oxidation inhibitor.
2. the preparation method of a modified terpene resin according to claim 1 is characterized in that:
(1) step 1: in container, add firpene, m-pentadiene, aluminum chloride, pentaerythritol ester gross weight 0.8-1 toluene doubly, with toluene is medium, polymerization in toluene, polymerization temperature-5-10 ℃, pressure is normal pressure, more a certain amount of firpene, m-pentadiene, aluminum chloride, pentaerythritol ester oxidation inhibitor is slowly splashed in the reaction mixture, drips off in 30-45 minute, constantly stir stirring reaction 2-8 hour during polymerization;
Step 2: the reaction mixture of step 1 is washed with 70-90 ℃ of water, divide the phase of anhydrating, distillating recovering solvent and oligopolymer get the faint yellow solid modified terpene resin.
3. according to claim 1 and 2 described modified terpene resins and preparation method thereof, it is characterized in that: firpene, m-pentadiene monomer intermittently or continuously drop into.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010258704 CN101891862A (en) | 2010-08-18 | 2010-08-18 | Modified terpene resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010258704 CN101891862A (en) | 2010-08-18 | 2010-08-18 | Modified terpene resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101891862A true CN101891862A (en) | 2010-11-24 |
Family
ID=43101232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010258704 Pending CN101891862A (en) | 2010-08-18 | 2010-08-18 | Modified terpene resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101891862A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898564A (en) * | 2012-11-01 | 2013-01-30 | 张道飘 | Method for preparing terpene resin |
| CN103834240A (en) * | 2014-03-19 | 2014-06-04 | 王勇 | TPE (Thermoplastic Polyolefin) rubber waterproof coating film and preparation method thereof |
| CN104045768A (en) * | 2013-03-12 | 2014-09-17 | 住友化学株式会社 | Conjugated diene based polymer, and polymer composition containing the polymer |
| CN104151467A (en) * | 2014-08-21 | 2014-11-19 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
| CN104341555A (en) * | 2013-07-29 | 2015-02-11 | 抚顺伊科思新材料有限公司 | Synthesis method for modified m-pentadiene resin |
| CN104877595A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Hot-melt adhesive |
| CN105622844A (en) * | 2016-03-24 | 2016-06-01 | 赣州泰普化学有限公司 | Modified terpene resin and preparation method thereof |
| CN111454399A (en) * | 2020-04-30 | 2020-07-28 | 厦门中坤化学有限公司 | Light-colored high-softening-point modified carene resin and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048124A (en) * | 1975-02-13 | 1977-09-13 | Nippon Zeon Co. Ltd. | Pressure sensitive adhesive |
| EP0260001A1 (en) * | 1986-08-21 | 1988-03-16 | Exxon Chemical Patents Inc. | Hydrogenated petroleum resins and their use in adhesives |
| CN1631916A (en) * | 2004-11-21 | 2005-06-29 | 蓝运泉 | Production method of terpene resin |
| CN1709927A (en) * | 2005-07-08 | 2005-12-21 | 广西大学 | Method for preparing colorless terpene resin |
| CN101503495A (en) * | 2009-02-24 | 2009-08-12 | 宁波职业技术学院 | Preparation of alpha-pinene modified C5 hydrocarbon resin |
| CN101613438A (en) * | 2009-07-29 | 2009-12-30 | 宁波甬华树脂有限公司 | A kind of preparation method of m-pentadiene modified DCPD petroleum resin |
-
2010
- 2010-08-18 CN CN 201010258704 patent/CN101891862A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048124A (en) * | 1975-02-13 | 1977-09-13 | Nippon Zeon Co. Ltd. | Pressure sensitive adhesive |
| EP0260001A1 (en) * | 1986-08-21 | 1988-03-16 | Exxon Chemical Patents Inc. | Hydrogenated petroleum resins and their use in adhesives |
| CN1631916A (en) * | 2004-11-21 | 2005-06-29 | 蓝运泉 | Production method of terpene resin |
| CN1709927A (en) * | 2005-07-08 | 2005-12-21 | 广西大学 | Method for preparing colorless terpene resin |
| CN101503495A (en) * | 2009-02-24 | 2009-08-12 | 宁波职业技术学院 | Preparation of alpha-pinene modified C5 hydrocarbon resin |
| CN101613438A (en) * | 2009-07-29 | 2009-12-30 | 宁波甬华树脂有限公司 | A kind of preparation method of m-pentadiene modified DCPD petroleum resin |
Non-Patent Citations (1)
| Title |
|---|
| 《广西化工》 19961231 王颖等 松节油制备高软化点萜烯树脂 第18-20页 1-3 第25卷, 第1期 2 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898564A (en) * | 2012-11-01 | 2013-01-30 | 张道飘 | Method for preparing terpene resin |
| CN102898564B (en) * | 2012-11-01 | 2015-07-22 | 张道飘 | Method for preparing terpene resin |
| CN104045768A (en) * | 2013-03-12 | 2014-09-17 | 住友化学株式会社 | Conjugated diene based polymer, and polymer composition containing the polymer |
| CN104045768B (en) * | 2013-03-12 | 2018-02-16 | 住友化学株式会社 | Conjugated diene polymer, and the polymer composition containing the polymer |
| CN104341555A (en) * | 2013-07-29 | 2015-02-11 | 抚顺伊科思新材料有限公司 | Synthesis method for modified m-pentadiene resin |
| CN104341555B (en) * | 2013-07-29 | 2017-11-10 | 抚顺伊科思新材料有限公司 | The synthetic method of modified pentadiene resin |
| CN103834240A (en) * | 2014-03-19 | 2014-06-04 | 王勇 | TPE (Thermoplastic Polyolefin) rubber waterproof coating film and preparation method thereof |
| CN104151467A (en) * | 2014-08-21 | 2014-11-19 | 梧州市嘉盈树胶有限公司 | Preparation method of terpene resin |
| CN104877595A (en) * | 2015-05-19 | 2015-09-02 | 广西众昌树脂有限公司 | Hot-melt adhesive |
| CN105622844A (en) * | 2016-03-24 | 2016-06-01 | 赣州泰普化学有限公司 | Modified terpene resin and preparation method thereof |
| CN111454399A (en) * | 2020-04-30 | 2020-07-28 | 厦门中坤化学有限公司 | Light-colored high-softening-point modified carene resin and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101891862A (en) | Modified terpene resin and preparation method thereof | |
| US4824921A (en) | Petroleum resins and their production | |
| AU2008224771B2 (en) | Adhesive composition for removable pressure sensitive adhesive label | |
| CN102391803A (en) | Colorless transparent hot-melt pressure sensitive adhesive (HMPSA) and preparation method thereof | |
| JP2011252156A (en) | Terpene resin- and hydrocarbon resin-based surfactant and aqueous dispersion of tackifier resin | |
| CN100513528C (en) | Prepolymer containing mixture of C10, C15, C20 olefin, preparation and application thereof | |
| CN100500718C (en) | Process for producing petroleum resin by hot polymerization | |
| CN104610892A (en) | Formula of environment-friendly particle hot-melt type pressure-sensitive adhesive and preparation method for adhesive | |
| CN102746472B (en) | Special modified polypropylene resin and preparation method thereof | |
| CN106715626A (en) | Pressure sensitive adhesives | |
| CN108285503B (en) | High-softening-point terpene resin and preparation method thereof | |
| CN102718927A (en) | Production method for coumarone resin | |
| US4636555A (en) | Petroleum resins and their production | |
| CN112266443A (en) | High-molecular petroleum resin for special functional membrane and preparation method thereof | |
| JPS63113046A (en) | Production of petroleum resin composition | |
| CN108752528A (en) | A kind of C9 hot polymerizations resin and its controllable preparation process of molecular weight and softening point | |
| CN102993386A (en) | Method for preparing modified C5 petroleum resin based on irradiation grafting | |
| US4245075A (en) | Carene modified petroleum resins | |
| CN110204657B (en) | Light-color C9 heat-polymerized petroleum resin product with high softening point and preparation process thereof | |
| CN109054702A (en) | A kind of integrated apparatus and integrated production method producing hot-fusible pressure-sensitive adhesive | |
| CN109400806A (en) | A kind of light color C9 hot polymerization petroleum resin products and its preparation process | |
| CN106699972B (en) | A kind of preparation method and its device of C5/C10 copolymer resins | |
| KR20160001424A (en) | Petroleum Resin, Adhesive Composition Comprising the Same and Adhesive Tape | |
| CN101974300A (en) | Water-based complex membrane sealing rubber and preparation method thereof | |
| CN102010481A (en) | Preparation method of light-color pentadiene petroleum resins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20101124 |